Pre-hydrotreatment method of reforming feedstocks

A treatment method and hydrotreating technology, which are applied in the treatment of hydrocarbon oil, refining to remove heteroatoms, petroleum industry, etc., can solve the problems of high cracking activity, unsuitable carrier, and reduce liquid yield, etc., and achieve high denitrification performance. , good chemical stability and thermal stability, strong anti-coking performance

Active Publication Date: 2013-12-04
PETROCHINA CO LTD
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Problems solved by technology

[0005] CN1267187C discloses a silica-alumina containing pseudo-boehmite structure, the carrier silica content is high, and the silicon-containing compound solution is directly or co-currently introduced into the pseudo-boehmite slurry, the purpose It is to increase the content of four-coordinated aluminum to increase the acid strength and acid amount of alumina. The prepared silicon-containing alumina has high cracking activity. However, the higher cracking activity is used as a hydrogenation catalyst carrier, which reduces the liquid yield.
However, the composite oxide prepared by this method has a large number of micropores, which is not suitable for use as a carrier for hydrotreating catalysts for low- and medium-distillate oils.

Method used

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  • Pre-hydrotreatment method of reforming feedstocks

Examples

Experimental program
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Effect test

preparation example Construction

[0055] Embodiment uses the preparation of catalyst 1~8:

[0056] Preparation of Catalyst 1:

[0057] Configure 2L concentration as 100gAl 2 o 3 / L of sodium metaaluminate solution is placed in the glue tank, the temperature of the glue tank is controlled at 45°C, and 65v% CO is introduced under stirring conditions. 2 Mixed gas of +35v% air, the flow rate of carbon dioxide in the mixed gas is 3Nm 3 / h. When the pH value reaches 10.0, stop feeding the mixed gas, and then age for 20 minutes to obtain pseudo-boehmite slurry.

[0058] Configuration 3L concentration is 80gAl 2 o 3 / L of sodium metaaluminate solution is placed in the gel tank, and then add 2L80gSiO 2 / L of sodium silicate solution, control the temperature of the glue tank at 30°C, and feed 60v% CO 2 Mixed gas of +40v% air, CO in the mixed gas 2 The flow rate is 3Nm 3 / h, the pH at the end point was controlled to be 9.0, and the amorphous silicon-aluminum slurry was obtained by aging for 15 minutes.

[0059...

Embodiment 1

[0100] The pre-hydrotreating reactor adopts an adiabatic fixed bed and uses catalyst 1. Carry out sulfuration of the catalyst first: add carbon disulfide to cyclohexane to make sulfurized oil with a sulfur content of about 1000 μg / g, and start to feed the sulfurized oil when the reactor is heated up to 240°C, the pressure is 2.5Mpa, and the volumetric space velocity of the sulfurized oil is 3.0h -1 , the hydrogen / sulfurized oil volume ratio is 300:1, and then the temperature is raised to 350°C at a heating rate of 10°C / h and maintained for 25h to complete the sulfurization treatment of the catalyst.

[0101] After the vulcanization treatment, switch to raw oil 1, the reaction temperature is 220°C, the reaction pressure is 2.4MPa, and the liquid space velocity is 11h -1 , the volume ratio of hydrogen to oil is 70, the operation is 200h, and the sulfur and nitrogen content in the product is sampled and analyzed every 24h. The results are shown in Table 3.

Embodiment 2

[0103] The pre-hydrotreating reactor adopts an adiabatic fixed bed and uses catalyst 2. Catalyst sulfide treatment method is the same as embodiment 1.

[0104] After the vulcanization treatment, switch to feedstock oil 2, the reaction temperature is 240°C, the reaction pressure is 2.5MPa, and the liquid space velocity is 10h -1 , the volume ratio of hydrogen to oil is 80, the operation is 200h, and the sulfur and nitrogen content in the product is sampled and analyzed every 24h. The results are shown in Table 3.

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Abstract

The invention provides a pre-hydrotreatment method of reforming feedstocks. The pre-hydrotreatment process undergoes in the conditions that: the reaction inlet is at a temperature of 200-320DEG C, the operation pressure is over 2.4MPa, the volume space velocity of fresh raw oil is 4-12h<-1>, and the volume ratio of hydrogen to oil is 50-300; the hydrotreatment catalyst employed takes silicon-containing alumina as the carrier, cobalt and molybdenum as the active constituents, boron and alkali metal and / or alkaline earth metal as the auxiliary agents, and the precursor of the silicon-containing alumina carrier is amorphous silica-alumina containing pseudo-boehmite, which is obtained by preparation of an amorphous silica-alumina slurry and a pseudo-boehmite slurry first, followed by mixing and ageing of the two slurries, and the post-treatments of filtering, washing and drying. The method of the invention can be used to treat catalytic reforming feedstocks of high sulfur and nitrogen content as well as high olefin content in a low pressure condition, and can provide qualified feedstocks with sulfur and nitrogen content both less than 0.5 microgram / gram for catalytic reforming units.

Description

technical field [0001] The invention relates to a reforming raw material prehydrotreating method, which is especially suitable for the hydrotreating of the feed of a catalytic reforming unit. Background technique [0002] Catalytic reforming process is one of the important processes in oil refining and petrochemical industry. 6 ~C 11 The naphtha distillate is used as the raw material, and the reformed oil rich in aromatics is produced through hydrogen-catalyzed reaction, and hydrogen is produced as a by-product. The catalytic reforming process usually uses double (multi) noble metal catalysts such as platinum-rhenium and platinum-iridium. In order to prevent catalyst poisoning, the sulfur and nitrogen content in the feed are required to be less than 0.5 μg / g. Therefore, the raw material needs to be pre-hydrotreated before entering the reforming unit to remove impurities in the raw oil that are harmful to the catalytic reforming catalyst, including sulfur, nitrogen, olefins...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C10G45/08C10G49/04B01J23/887
Inventor 康宏敏向永生郑云弟蒋彩兰梁顺琴林宏柏介军马好文王书峰王廷海孙利民王宗宝潘曦竹蔡小霞吕龙刚
Owner PETROCHINA CO LTD
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